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WO2012043790A1 - Objet moulé par injection, résistant aux chocs, très réfléchissant et dépourvu de revêtement et son processus de production - Google Patents

Objet moulé par injection, résistant aux chocs, très réfléchissant et dépourvu de revêtement et son processus de production Download PDF

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Publication number
WO2012043790A1
WO2012043790A1 PCT/JP2011/072548 JP2011072548W WO2012043790A1 WO 2012043790 A1 WO2012043790 A1 WO 2012043790A1 JP 2011072548 W JP2011072548 W JP 2011072548W WO 2012043790 A1 WO2012043790 A1 WO 2012043790A1
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WIPO (PCT)
Prior art keywords
mass
injection
molded product
rubber component
copolymer
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PCT/JP2011/072548
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English (en)
Japanese (ja)
Inventor
藤沢　朋幸
美穂子 山本
博治 板谷
Original Assignee
旭化成ケミカルズ株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45893227&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012043790(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to EP11829343.0A priority Critical patent/EP2623289A4/fr
Priority to CN201180047731.6A priority patent/CN103153573B/zh
Priority to US13/824,827 priority patent/US9273204B2/en
Priority to KR1020137006376A priority patent/KR101466525B1/ko
Priority to JP2012536578A priority patent/JP5793501B2/ja
Publication of WO2012043790A1 publication Critical patent/WO2012043790A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

  • the present invention relates to an unpainted, high-definition, impact-resistant injection-molded article having high sharpness and excellent impact resistance, and a method for producing the same.
  • Thermoplastic resins imparted with impact resistance are widely used in home appliances, game machines, automobile interior materials, and the like.
  • products using these resins as materials have been required to have high aesthetics in addition to performances such as strength and impact resistance.
  • Vividness refers to the sharpness of an image reflected on the surface. For example, you can think of an image reflected on a piano or an image reflected on a high-grade black-painted car. I can feel it strongly. There is a strong demand for such sharpness, and various measures are taken by material manufacturers and the like.
  • Patent Document 1 a method is known in which a resin surface is subjected to a treatment for increasing the affinity with a paint to be applied to the resin so as to impart a clear image.
  • Patent Document 2 Also known is a method of imparting clarity to the surface by applying and curing a thermosetting resin or ionizing radiation curable resin on the surface to form a hard coat layer.
  • JP-A-5-43632 Japanese Patent Laid-Open No. 10-235771
  • Patent Document 1 the invention described in Patent Document 1 is complicated because it needs to be painted. In addition, all organic solvents such as thinner, which accounts for about half of the paint, are released into the atmosphere as volatile organic compounds, and the paint adhering to the injection molded product is 30% to 70%, and the rest are all discarded. Because it becomes a product, it has a problem that it is environmentally unfavorable.
  • An object of the present invention is to provide an injection molded product that has impact resistance and exhibits excellent sharpness without being painted, and a method for producing the same.
  • the present inventors have made an injection molded product in which a rubber component is dispersed in a thermoplastic resin, and the rubber component has a linear expansion coefficient in a specific range as an injection molded product.
  • the present inventors have found that the above problems can be solved, and have completed the present invention.
  • the present invention it is possible to achieve high image quality as special coating without requiring complicated processes such as painting and formation of a surface coat layer for applications such as home appliances, game machines, and automobile interior materials. It is possible to obtain a non-painted, high-definition, impact-resistant injection-molded product that has both an impact resistance and a scratch resistance.
  • the present invention is as follows.
  • Unpainted, high-definition, impact-resistant injection-molded product with the characteristics of [2] The unpainted high-definition impact-resistant injection-molded product according to [1], wherein the rubber polymer part of the rubber component (A) has a mass average particle diameter of 0.1 to 1.2 ⁇ m.
  • [3] The unpainted high-definition impact-resistant injection-molded article according to any one of [1] or [2], wherein the increase rate of the L * value by the fiber friction test is 60% or less.
  • [5] The method for producing an unpainted high-definition impact-resistant injection-molded product according to any one of [1] to [4], wherein the molding is performed using a mold having a surface roughness Ra of 0.02 ⁇ m or less.
  • the rubber component (A) contained in the injection-molded article of the present invention consists of a rubbery polymer and / or a graft copolymer containing a rubbery polymer and a graft component.
  • the rubbery polymer not only imparts impact resistance to the injection molded product, but also helps to release the injection molded product from the mold. Moreover, by using it in combination with the thermoplastic resin (B), it serves to impart both impact resistance and sharpness to the injection molded product.
  • the rubbery polymer include diene rubber, acrylic rubber, and ethylene rubber.
  • polybutadiene polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, and acrylonitrile-butadiene copolymer are preferably used from the viewpoint of impact resistance.
  • the rubbery polymer may have a uniform composition, may contain polymers having different compositions, or may have a continuously changing composition.
  • the graft component is one or more selected from aromatic vinyl monomers, vinyl cyanide monomers, and acrylic monomers. It is preferable that the polymer containing the monomer is bonded to the rubbery polymer.
  • the graft component may contain other monomers that can be copolymerized in addition to these monomers.
  • the graft ratio is preferably 200% or less, more preferably 50 to 170%, and still more preferably 60 to 150%. By setting the graft ratio within this range, the linear expansion coefficient of the rubber component (A) can be controlled to 12.5 ⁇ 10 ⁇ 5 to 19 ⁇ 10 ⁇ 5 / ° C.
  • the graft ratio can be defined by a mass ratio with respect to the mass of the rubber polymer of the graft component graft copolymerized with the rubber polymer.
  • the graft ratio of the rubber component (A) is determined by removing the solvent-soluble component from the injection-molded product using a solvent such as acetone, taking out the rubber component (A) as the solvent-insoluble component, and taking a Fourier transform infrared spectrophotometer (FT). The rubber component and other components can be analyzed by -IR) and obtained based on the result.
  • FT Fourier transform infrared spectrophotometer
  • the rubber component (A) in the injection-molded product of the present invention takes a form dispersed in the continuous phase of the thermoplastic resin (B).
  • the shape may be indefinite, rod-shaped, flat plate, or particle shape, but from the viewpoint of impact resistance, the particle shape is more preferable.
  • any of the cases where several aggregates are dispersed can be taken, but each one is independent in terms of impact resistance. Is preferable.
  • the size of the rubber-like polymer contained in the rubber component (A) dispersed in the thermoplastic resin is 0.1 ⁇ m or more in terms of a mold release effect when producing an injection molded product, as a mass average particle diameter, and It is preferably 1.2 ⁇ m or less from the viewpoint of the sharpness of the surface of the injection molded product. More preferred is 0.15 to 0.8 ⁇ m, further preferred is 0.15 to 0.6 ⁇ m, and particularly preferred is 0.2 to 0.4 ⁇ m.
  • the mass average particle diameter can be obtained by preparing an ultrathin section from an injection-molded product, observing it with a transmission electron microscope (TEM), and performing image analysis on an arbitrary range of 50 ⁇ m ⁇ 50 ⁇ m of the ultrathin section.
  • TEM transmission electron microscope
  • the mass average particle diameter corresponds to the diameter of the rubbery polymer when it is spherical, and when it is not spherical, it is the average value of the longest diameter and the shortest diameter.
  • the rubber component (A) is composed of only a rubber component in the case of a rubbery polymer, but in the case of a rubbery polymer containing a graft component, for example, the resin component is phase-separated inside the rubbery polymer.
  • the mass average particle diameter of the rubbery polymer portion in the case of particles containing occlusion is measured in a state including occlusion.
  • the rubber component (A) needs to have a specific coefficient of linear expansion when taken out from the injection molded product.
  • the linear expansion coefficient of the rubber component (A) is 12.5 ⁇ 10 ⁇ 5 to 19 ⁇ 10 ⁇ 5 / ° C., preferably 12.5 ⁇ 10 ⁇ 5 to 17 ⁇ 10 ⁇ 5 / ° C.
  • the resin When the resin is molded, it is cooled from a high temperature state in a molten state to a solid state temperature. At that time, the rubber component that has been compressed and deformed at a high temperature recovers its deformation upon cooling. Try to let them. This process affects the surface of the injection-molded product, and the clarity of the injection-molded product decreases. Therefore, by setting the linear expansion coefficient of the rubber component within a certain range, it is possible to make the rubber component difficult to be deformed, and as a result, it is possible to prevent a reduction in definition.
  • the measurement of the linear expansion coefficient of the rubber component (A) may be performed by isolating the rubber component (A) from a composition containing the rubber component (A) or an injection molded product.
  • a resin component is dissolved but a solvent that does not dissolve the rubber component is selected, the resin part is dissolved from the injection-molded product, and the rubber component (A) is taken out.
  • the rubber component is made of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, etc.
  • the thermoplastic resin (B) is made of polystyrene, MS resin, AS resin, acrylic resin, or the like.
  • acetone can be used. Even when the injection-molded article contains a material made of a rubbery polymer or a thermoplastic resin other than those described above, it is easy to select an appropriate solvent from each composition.
  • the linear expansion coefficient of the rubber component (A) can be controlled and reduced by the following method. 1) Increase the graft ratio of the rubber component (A). 2) Increase the degree of crosslinking of the rubbery polymer constituting the rubber component (A). 3) The glass transition temperature (Tg) of the rubbery polymer constituting the rubber component (A) is increased.
  • the method 1) it is possible to control the linear expansion coefficient without largely depending on the degree of crosslinking of the rubbery polymer or Tg.
  • the graft ratio can be adjusted by increasing or decreasing the mass of the monomer that performs graft polymerization with respect to the mass of the rubbery polymer when the rubber component (A) is prepared.
  • a swelling index may be used as an index indicating the degree of crosslinking of the rubbery polymer.
  • a preferred swelling index is 10 to 80%, more preferably 15 to 60%.
  • the coefficient of linear expansion of the rubber component (A) can be controlled within a preferable range.
  • the swelling index is controlled by increasing the polymerization temperature, increasing the polymerization conversion at the end of the polymerization, and decreasing the monomer / polymer concentration ratio during the polymerization.
  • Such a method can be employed, and in this way, the swelling index is reduced and the degree of crosslinking can be increased.
  • the swelling index can be reduced by copolymerizing a crosslinkable monomer such as divinylbenzene.
  • the Tg of the rubbery polymer is preferably about ⁇ 100 to 0 ° C. from the viewpoint of impact resistance. More preferably, it is ⁇ 20 to ⁇ 90 ° C.
  • the linear expansion coefficient can be reduced by adjusting the composition of the monomer constituting the rubber polymer to bring the Tg of the rubber polymer close to the upper limit of 0 ° C.
  • Examples of a method for controlling the Tg of the rubbery polymer include a method of using a copolymer as the rubbery polymer and adjusting the composition ratio of the copolymer. For example, in the case of a styrene-butadiene block copolymer, the Tg of the rubbery polymer can be increased by lowering the butadiene ratio in the block portion mainly composed of butadiene.
  • the above methods 1) to 3) can be used alone or in combination.
  • the method of controlling by the graft ratio is preferable because it is easy to balance the sharpness and the impact resistance.
  • the thermoplastic resin (B) in the present invention is a resin that can be injection molded, and can be used together with the rubber component (A) to impart impact resistance and sharpness to the injection molded product.
  • the strength, hardness and heat resistance necessary for practical use can be imparted to the injection molded product.
  • an amorphous thermoplastic resin is preferable from the viewpoint of miscibility with the rubber component (A).
  • Tg glass transition temperature
  • an injection molded product having practically necessary strength, hardness and heat resistance can be obtained.
  • resins include polystyrene, AS resin, methacrylic resin, MS resin, polycarbonate resin, aromatic polyether resin, and the like. These may be used alone or in combination.
  • the thermoplastic resin (B) in the present invention preferably has a reduced viscosity ( ⁇ sp / c) in the range of 0.2 to 1.5 dl / g. More preferably, it is 0.3 to 0.8 dl / g. When the reduced viscosity is 0.2 or more, impact resistance and strength are not lowered, and when the reduced viscosity is 1.5 or less, sufficient moldability can be obtained.
  • the amount of the rubber component (A) is preferably 20 to 50% by mass, more preferably Is 25 to 40% by mass.
  • 20% by mass or more is preferable in terms of impact resistance and mold release of the molded product when injection molding is performed.
  • thermoplastic resin (B) and the composition of the graft component in the rubber component (A) are adjusted to increase the compatibility, the dispersion state of the rubbery polymer becomes good, and the injection molding is performed. It is possible to balance the impact resistance, sharpness and scratch resistance of products. Examples of preferred combinations of the thermoplastic resin (B) and the graft component in the rubber component (A) are shown below.
  • the graft portion in the rubber component (A) is also preferably a composition containing a vinyl cyanide monomer, and the rubber component (A)
  • the amount of the vinyl cyanide monomer in the graft component and the thermoplastic resin (B) is preferably 15% by mass to 45% by mass, respectively.
  • thermoplastic resin (B) is a mixture of a copolymer composed of an aromatic vinyl monomer and a vinyl cyanide monomer, and a copolymer composed of a methacrylic monomer and an acrylic monomer
  • the amount of the vinyl cyanide monomer in the graft component in the rubber component (A) and the thermoplastic resin (B) is preferably 15 to 30% by mass.
  • the methyl methacrylate content in the acrylic monomer copolymer is preferably in the range of 75 to 98% by mass. More preferably, it is 85 to 98% by mass.
  • the thermoplastic resin (B) is a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, or an aromatic vinyl monomer, a vinyl cyanide monomer, an acrylic resin
  • the amount of the vinyl cyanide monomer in the graft component in the rubber component (A) and in the thermoplastic resin (B) is 30 to 45 masses, respectively. % Is preferred.
  • the acrylic monomer is included, the amount of the acrylic monomer in the graft component in the rubber component (A) and the thermoplastic resin (B) is 5 to 20 masses in terms of sharpness. % Is preferred. Since the presence of the acrylic monomer improves fluidity, it becomes easy to obtain a high-definition injection molded product. Of these, butyl acrylate and butyl methacrylate are particularly preferably used.
  • the injection molded product of the present invention may contain a sliding aid (C) as a raw material other than the rubber component (A) and the thermoplastic resin (B).
  • the purpose of the sliding aid is to impart lubricity to the surface of the injection molded product.
  • the content of the sliding aid (C) is preferably 0.05 to 2% by mass with respect to the total mass of the rubber component (A) and the thermoplastic resin (B) from the viewpoint of impact resistance.
  • sliding aid (C) examples include lubricants such as aliphatic metal salts, polyolefins, polyester elastomers, polyamide elastomers, and the like.
  • the aliphatic metal salt and the like it is preferable from the viewpoint of scratch resistance that at least one fatty acid metal salt and at least one lubricant having an amide group or an ester group are blended.
  • the fatty acid metal salt is a salt of a metal and a fatty acid containing at least one selected from sodium, magnesium, calcium, aluminum, and zinc.
  • a stearic acid-based metal salt Particularly preferred is a stearic acid-based metal salt. Specifically, calcium stearate is preferred in terms of scratch resistance.
  • polyolefins examples include compositions produced from at least one of ethylene, propylene, ⁇ -olefin, and the like, and these include compositions derived from the composition as a raw material.
  • polypropylene ethylene-propylene copolymer
  • polyethylene high density, low density, linear low density
  • oxidized polyolefin oxidized polyolefin
  • graft polymerized polyolefin oxidized polyolefin
  • oxidized polyolefin wax and polyolefin grafted with styrene resin are preferred from the viewpoint of scratch resistance, and more preferably polypropylene wax, polyethylene wax, oxidized polypropylene wax, oxidized polyethylene wax, acrylonitrile-styrene copolymer.
  • polypropylene wax polyethylene wax
  • oxidized polypropylene wax oxidized polyethylene wax
  • acrylonitrile-styrene copolymer graft polyethylene
  • styrene polymer graft polypropylene graft polyethylene
  • polyester elastomer examples include polyesters obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, ring-opening polycondensation of a polycondensation lactone compound of an oxycarboxylic acid compound, or polycondensation of a mixture of these components. Either a homopolyester or a copolyester may be used.
  • dicarboxylic acid compound examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 3 Aromatic dicarboxylic acids such as sodium sulfoisophthalate, aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic Examples thereof include aliphatic dicarboxylic acids such as acid, succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid, and mixtures of these di
  • dicarboxylic acid compounds can also be used in the form of an ester-forming derivative, for example, a lower alcohol ester such as dimethyl ester.
  • these dicarboxylic acid compounds can be used alone or in combination of two or more.
  • terephthalic acid isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferably used from the viewpoints of polymerizability, color tone and impact resistance.
  • dihydroxy compound examples include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, 2,2-bis (4- Hydroxyphenyl) propane and the like, and these polyoxyalkylene glycols and their alkyl, alkoxy or halogen substituents. These dihydroxy compounds can be used alone or in combination of two or more.
  • oxycarboxylic acid compound examples include oxybenzoic acid, oxynaphthoic acid, diphenyleneoxycarboxylic acid and the like, and these alkyl, alkoxy and halogen substituted products are also included. These oxycarboxylic acid compounds can be used alone or in combination of two or more. A lactone compound such as ⁇ -caprolactone can also be used for the production of a polyester elastomer.
  • polyamide elastomer examples include aminocarboxylic acids or lactams having 6 or more carbon atoms, and nylon mn salts having m + n of 12 or more.
  • the hard segment (X) includes ⁇ -aminocaproic acid, ⁇ -aminoenanoic acid, ⁇ - Aminocarboxylic acids such as aminocaprylic acid, ⁇ -aminobergonic acid, ⁇ -aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid; lactams such as caprolactam laurolactam, nylon 6,6, nylon 6,10, Nylon salts such as nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11,12, nylon 12,10, nylon 12,12 and the like can be mentioned.
  • soft segment (Y) such as polyol
  • soft segment (Y) such as polyol
  • examples of the soft segment (Y) include polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and ethylene oxide.
  • examples thereof include a block or random copolymer of propylene oxide and a block or random copolymer of ethylene oxide and tetrahydrofuran.
  • the number average molecular weight of these soft segments (Y) is 2.0 ⁇ 10 2 to 6.0 ⁇ 10 3 , preferably 2.5 ⁇ 10 2 to 4.0 ⁇ 10 3 .
  • poly (alkylene oxide) glycol may be aminated or carboxylated for use.
  • sliding aids (C) a combination of a stearic acid metal salt and a wax is particularly preferable in terms of scratch resistance.
  • an acid-modified or epoxy-modified modified resin may be mixed for the purpose of improving the compatibility.
  • the thermoplastic resin (B) is a copolymer of monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and acrylic monomers. In this case, those obtained by copolymerizing a vinyl monomer containing a carboxyl group or a glycidyl group can be used.
  • vinyl monomer containing a carboxyl group examples include unsaturated compounds containing a free carboxyl group such as acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, maleic anhydride, itaconic anhydride, and chloromaleic anhydride.
  • unsaturated compounds containing an acid anhydride-type carboxyl group such as acid and citraconic anhydride.
  • acrylic acid, methacrylic acid, and maleic anhydride are preferable in terms of scratch resistance.
  • Examples of the vinyl monomer containing a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, methyl glycidyl ether, and methyl glycidyl methacrylate.
  • glycidyl methacrylate is scratch resistant. It is suitable.
  • a phosphite-based, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based and cyanoacrylate-based ultraviolet absorber and antioxidant within the range not impairing the effects of the present invention
  • Higher fatty acids, acid esters and acid amides, lubricants and plasticizers such as higher alcohols, montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stellar amide and ethylene wax
  • release agents such as phosphorus Anti-coloring agents such as acid salts and hypophosphites, nucleating agents, amine-based, sulfonic acid-based, polyether-based antistatic agents, 1,3-phenylenebis (2,6-dimethylphenyl phosphate), Tetraphenyl-m-phenylenebisphosphate, phenoxyphosphoryl, fluorine Phosphorus-based flame retardant such as Bruno carboxymethyl phosphazen
  • colorants such as inorganic pigments, organic pigments, metallic pigments, and dyes may be added.
  • colorants those in which the color of the injection-molded product is white, black, red are preferably used because they give a particularly high-class feeling to the design of the injection-molded product.
  • inorganic pigments examples include titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine, cobalt blue, chromium oxide, spinel green, lead chromate pigments, and cadmium pigments.
  • organic pigments examples include azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, and perylenes.
  • azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments
  • phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green
  • isoindolinone pigments examples of quinophthalone pigments, quinacridone pigments
  • perylenes examples include condensed polycyclic pigments such as pigments, anthraquinone pigments, perinone pigments, and dioxazine violet.
  • metallic pigments examples include flake-like aluminum metallic pigments, spherical aluminum pigments used to improve the weld appearance, mica powder for pearl-like metallic pigments, and other polyhedral particles of inorganic substances such as glass. And the like coated with plating or sputtering.
  • dyes include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, azines
  • dyes include dyes, oxazine dyes, thiazine dyes, sulfur dyes, amino ketone / oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes.
  • colorants can be used alone or in combination of two or more.
  • the addition amount of these is preferably 0.05 to 2% by mass, more preferably 0.1 to 1.5% by mass in terms of color tone.
  • the injection molded product of the present invention has a sharpness of 60 to 100% and a notched Charpy impact strength of 5 to 60 kJ / m 2 .
  • the sharpness is preferably 90 to 100%, more preferably 95% or more.
  • Charpy impact strength notched preferably 7 ⁇ 50kJ / m 2, more preferably 8 ⁇ 30kJ / m 2.
  • the sharpness is what makes the injection-molded product feel aesthetic, and if it is 60% or more, it usually gives an excellent sense of luxury.
  • the Charpy impact strength with a notch is 5 kJ / m 2 or more, and it can be used practically without problems in home appliances, game machines, automobile interior materials, and the like. On the other hand, by setting it to 60 kJ / m 2 or less, it becomes easy to achieve both clarity and clarity.
  • the injection-molded article of the present invention has been realized to be unpainted and high-definition, but practically, by actions such as cleaning and wiping off dirt, which is usually performed in daily use, It is necessary that the sharpness does not deteriorate.
  • the reason that the sharpness is deteriorated by the wiping operation is that fine scratches are generated on the surface of the injection molded product.
  • the fiber friction test can be used as a measure of the sharpness retention ability, i.e., scratch resistance.
  • the fiber friction test is a test in which the surface of an injection-molded product is rubbed with a tissue paper to determine the degree of damage.
  • the increase amount of the L * value on the surface of the injection molded product is preferably 60% or less before and after this test, there is no practical problem in daily use. More preferably, the increase amount of the L * value is 30% or less, and particularly preferably 5% or less.
  • the linear expansion coefficient of the rubber component (A) is in the range of 12.5 ⁇ 10 ⁇ 5 to 19 ⁇ 10 ⁇ 5 in order to make the increase amount of the L * value on the surface of the injection molded product a preferable range. It is sufficient to select a thermoplastic resin (B) having a high hardness.
  • the Rockwell hardness is preferably 40 to 105 on the M scale, and more preferably 50 to 105.
  • thermoplastic resin (B) examples include, for example, i) a copolymer of at least two monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and acrylic monomers.
  • aromatic vinyl monomers examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and pt-butylstyrene, vinylnaphthalene, etc. Is mentioned. Of these, styrene and ⁇ -methylstyrene are preferably used. These can be used alone or in combination of two or more.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, and ethacrylonitrile. Among them, acrylonitrile is preferably used. These can be used alone or in combination of two or more.
  • acrylic monomers examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, ( N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6- (meth) acrylate
  • Unsaturated carboxylic acid alkyl ester monomers such as pentahydroxyhexyl and (meth) acrylic acid 2,3,4,5-tetrahydroxypentyl, (meth) acrylic acid, and the like. Can be used in combination.
  • the content of methyl methacrylate in the acrylic monomer is preferably 80 to 94% by mass in terms of sharpness. More preferably, it is 85 to 91% by mass.
  • thermoplastic resin (B) When using a copolymer of a monomer selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and an acrylic monomer as the thermoplastic resin (B), if necessary, You may use what copolymerized the other monomer which can be copolymerized.
  • other copolymerizable monomers include N-substituted maleimide monomers such as maleic anhydride, N-phenylmaleimide and N-methylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. . These can be used alone or in combination of two or more. Among these, N-phenylmaleimide is preferable in that heat resistance can be imparted without impairing other physical properties.
  • the polycarbonate resin either an aromatic homopolycarbonate or an aromatic copolycarbonate can be used.
  • the production method include a phosgene method in which phosgene is blown into a bifunctional phenol compound in the presence of a caustic alkali and a solvent, and a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst. be able to.
  • examples of the bifunctional phenolic compound include 2,2′-bis (4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3,5-diphenyl) Butane, 2,2′-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4- Hydroxyphenyl) ethane, etc., especially 2,2′-bis (4-hydroxyphenyl) propane [bisphenol A] etc., which can impart hardness to this It is preferable to use a compound having a group is introduced structures.
  • the bifunctional phenolic compound may be used alone or in combination.
  • the polycarbonate resin can be used alone, but is composed of at least two or more monomers selected from the above-mentioned aromatic vinyl monomers, vinyl cyanide monomers, and acrylic monomers. Use in combination with a copolymer is preferred from the viewpoint of the hardness of the thermoplastic resin (B).
  • a polycarbonate copolymer having high hardness specifically, for example, if it is an aromatic copolycarbonate having high hardness, the copolymer described in JP-A-8-183852, ie, two or more aromatics
  • a copolycarbonate containing units derived from a dihydroxy compound and containing a structural unit represented by the following formula [I] in an amount of 50 to 99 mol% can be used.
  • polyphenylene ether When polyphenylene ether is used, the production method thereof is, for example, U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358, Japanese Patent Application Laid-Open No. 50-51197. And the production methods described in JP-A-63-152628 and the like. That is, polyphenylene ether is obtained by oxidative coupling of a phenol compound, and includes a homopolymer and a copolymer.
  • polyphenylene ether examples include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2- Methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), etc., and the co-polymerization of 2,6-dimethylphenol with other phenols
  • a compound for example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in Japanese Patent Publication No. 52-17880
  • Polyphenylene ether copolymers may also be mentioned.
  • polyphenylene ether is poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a mixture thereof. It is.
  • thermoplastic resin (B) these resins can be used alone or in combination.
  • the resistance value at 20 g in a continuous load type surface measuring machine is 3 gf or less. More preferably, it is 2.5 gf or less, and most preferably 2.0 gf or less. In order to reduce the value measured by the continuous load type surface measuring instrument, it is effective to reduce the linear expansion coefficient of the rubber component (A).
  • the injection molded product of the present invention preferably has a content of volatile components having a boiling point of 200 ° C. or less of 1500 ppm or less.
  • the volatile content is 1500 ppm or less, the reduction in sharpness is small even after a long period of time.
  • the volatile matter contained in the thermoplastic resin (B) and rubber component is a raw material monomer remaining in the resin or rubber, a solvent used in the production process, etc., for example, an aromatic vinyl monomer, vinyl cyanide Monomer, acrylic monomer, and the like. Or the additive etc. which contain the component whose boiling point is 200 degrees C or less are mentioned.
  • the injection molded product of the present invention preferably has a surface roughness (Ra) of 0.1 or less.
  • Ra surface roughness
  • the surface roughness of the injection molded product varies depending on the surface roughness of the mold and the molding conditions. For example, when the surface roughness of the mold is small, the mold temperature is increased, and the molding pressure is decreased, the surface roughness of the injection molded product tends to decrease.
  • a polymer having a plurality of Tg When a polymer having a plurality of Tg is used as the rubber polymer, it can be produced by polymerizing different monomer compositions in multiple stages. It is preferable to produce by multistage polymerization using an emulsion polymerization method.
  • the rubbery polymer when it is a polymer having a composition gradient, it can be polymerized by continuously changing the monomer composition. For example, in emulsion polymerization, it can manufacture using what is called a power feed method.
  • the rubber polymer is a block copolymer of an aromatic vinyl monomer and a diene vinyl monomer, for example, a styrene-butadiene block copolymer, it is produced by living anion polymerization in a solution. can do.
  • a method for producing a rubbery polymer containing a graft component methods such as bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, and emulsion polymerization can be used.
  • a thermal decomposition type initiator that generates radicals by heat or a redox type initiator can be used.
  • emulsion polymerization method for example, a rubbery polymer obtained separately by emulsion polymerization can be used, and a method of emulsion polymerization of a vinyl monomer can be used.
  • the graft portion obtained here is preferably compatible with the thermoplastic resin (B) in terms of impact resistance.
  • the graft polymerization may be continuously performed in the same reactor, or the rubber particles may be once isolated as latex and then graft polymerization may be performed again.
  • one or two monomers selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and an acrylic monomer are added to the polybutadiene latex obtained by emulsion polymerization.
  • a method for obtaining the above-described graft polymerization in which radicals are initiated can be mentioned.
  • the one or more monomers include styrene and acrylonitrile, styrene and methyl methacrylate, styrene, methyl methacrylate, and acrylonitrile.
  • the radical initiator initiators such as peroxodisulfate and t-butylperoxy-2-ethylhexanoate can be used.
  • a diene monomer is subjected to living anion polymerization to obtain an uncrosslinked rubber polymer, and this is then combined with a styrene monomer or a styrene-acrylonitrile monomer.
  • a method obtained by precipitating a composite of a rubber component and a high Tg resin component by performing polymerization can be used.
  • thermoplastic resin composition (B) examples include bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, and emulsion polymerization.
  • a copolymer of at least two monomers selected from aromatic vinyl monomers, vinyl cyanide monomers and acrylic monomers it is possible to produce them by radical polymerization. preferable.
  • the injection molded product of the present invention is manufactured by a process of melting the thermoplastic resin (B) and kneading the rubber component (A) to manufacture a composition, and an injection molding process.
  • the rubber component (A) and the thermoplastic resin (B) are, for example, melt kneading using an open roll, an intelligent mixer, an internal mixer, a kneader, a continuous kneader with a twin-screw rotor, or an extruder such as an extruder. It can be kneaded by a method or the like. Single or twin screw extruders are commonly used.
  • thermoplastic resin (B) is supplied from the main inlet installed on the screw base side, and rubber is supplied from the secondary inlet installed between the main inlet and the extruder tip.
  • the preferred melt-kneading temperature varies depending on the type of the thermoplastic resin (B), but is the cylinder set temperature, for example, about 290 to 330 ° C. for PPE and about 180 to 270 ° C. for AS resin.
  • the cylinder temperature should be 30 to 200 ° C. in the supply zone, and the temperature of the kneading zone in which melt kneading is performed.
  • the melt kneading time is preferably about 0.5 to 5 minutes.
  • the content of volatile components having a boiling point of 200 ° C. or less in the resin composition is preferably 1500 ppm or less at the stage of supplying the resin composition to an injection molding machine.
  • the extruded resin can be directly cut into pellets or formed into strands and then cut with a pelletizer for pelletization.
  • the shape of the pellet can be a general shape such as a cylinder, a prism, or a sphere, but a cylinder is preferable.
  • the injection molded product of the present invention is molded by an injection molding machine.
  • injection molding include injection compression molding, gas assist molding using nitrogen gas or carbon dioxide gas, and high-speed heat cycle molding in which the mold temperature is increased. These can be used in combination.
  • Preferred are gas assist molding, high speed heat cycle molding, and a combination of gas assist molding and high speed heat cycle molding.
  • the gas assist molding referred to here is generally known injection molding using nitrogen gas or carbon dioxide gas.
  • a resin is injected into a mold cavity.
  • a method of injecting a pressurized gas into the molded body a method of injecting a pressurized gas into a cavity corresponding to one side of the molded body after injecting resin into the mold cavity, for example, as in Japanese Patent No. 3819972,
  • a thermoplastic resin is filled with a gas in advance as in Japanese Patent No. 3349070.
  • the method of press-fitting pressurized gas into the cavity corresponding to one side of the molded body is preferable.
  • gas assist is preferred as the pressure retention for preventing sinking and warping.
  • the mold temperature is relatively high, so that burrs are easily generated, and if the holding time is not lengthened, sinking and warping cannot be prevented.
  • the pellets produced as described above can be used as a kneaded product with the rubber component (A) and the thermoplastic resin (B), and other additives, and an injection molded product can be molded by an injection molding machine.
  • a mold finished with a file of # 4000 or more, preferably # 12000 or more is used as the mold of the molding machine.
  • the arithmetic average surface roughness Ra of the mold is preferably 0.02 ⁇ m or less, more preferably 0.01 ⁇ m or less.
  • the method for making the surface of the mold like this is not particularly limited, and it can be adjusted by polishing with an ultrasonic polishing machine or a manual work with a diamond file, a grindstone, a ceramic grindstone, a ruby grindstone, a GC grindstone, or the like. it can.
  • the steel material of the mold to be used is preferably a quenched and tempered steel of 40 HRC or more, more preferably 50 HRC or more.
  • a chrome plated mold may be used, or a chrome plated mold may be used on the polished mold as described above.
  • the mold temperature is preferably set near the Vicat softening point of the kneaded product of the rubber component (A) and the thermoplastic resin (B) from the viewpoint of sharpness.
  • the Vicat softening point in accordance with ISO 306 is preferably ⁇ 25 to + 20 ° C., more preferably ⁇ 15 to + 5 ° C. In the case of this condition, the transferability to the cavity surface is improved, and an injection-molded product with more excellent sharpness can be obtained.
  • the cooling rate of the surface of the molded body has a great influence on the sharpness of the molded body, and is preferably cooled at 1 to 100 ° C./second. Furthermore, 30 to 90 ° C./second is preferable, and 40 to 80 ° C./second is particularly preferable.
  • a molding method in which the mold temperature is raised or lowered using a mold having a steam pipe or a heating wire built therein, or a molding method using supercritical CO 2 can be preferably used.
  • the resin (the kneaded material) at the time of injection molding is preferably molded at a temperature suitable for the resin to be molded.
  • a resin temperature of 220 to 260 ° C. is preferable for an ABS resin, rubber-modified polystyrene, and the like, and a methyl methacrylate resin, and a resin temperature of 260 to 300 ° C. is preferable for a resin containing polycarbonate.
  • the injection-molded product of the present invention preferably has an injection speed of 1 to 50 mm / s, more preferably 5 to 30 mm / s, from the viewpoint of scratch resistance.
  • the injection-molded article of the present invention is manufactured by the above method, but promotes the kneading of the thermoplastic resin (B) and the rubber component (A), and the rubber component (A) is well dispersed in the thermoplastic resin.
  • the following method can be used.
  • the rubber component When melt-kneading the rubber component and the thermoplastic resin, for example, when the rubber component is in a bulk form, it is preferable to refine the rubber component in advance.
  • a method of finely crushing the rubber component (A) cooled and solidified to a temperature of Tg or less For cooling to a temperature below Tg, for example, liquid nitrogen, dry ice / acetone solvent, or the like can be used.
  • the cooled rubber component can be refined by putting it into a mill, hitting it with a hammer, or the like.
  • the polymer in the case of a latex in which both the rubber component (A) and the thermoplastic resin (B) are obtained by emulsion polymerization, after mixing in the latex state, the polymer can be aggregated and the mixture can be taken out.
  • a phase between a part of the rubber component (A) and the thermoplastic resin (B) can be used.
  • solubility There are ways to increase solubility. The following is mentioned as a method of improving compatibility.
  • the rubber component (A) is in the form of fine particles, for example, a fine rubber obtained by pulverization
  • a method of coating the surface of the fine rubber with a thermoplastic resin may be mentioned.
  • the rubber surface can be coated by immersing the refined rubber in a thermoplastic resin solution and then drying the refined rubber.
  • the present invention can be applied when the rubber component (A) is a rubbery polymer containing no graft component.
  • the rubber polymer of the rubber component (A) is a copolymer block
  • a combination in which the block portion and the thermoplastic resin (B) are highly compatible is used.
  • a polyphenylene ether resin alone, an alloy of a polyphenylene ether resin and a polystyrene resin, or a polystyrene resin can be used.
  • compatibilizer for the rubber component (A) and the thermoplastic resin (B)
  • examples of the compatibilizer include a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer. Or a hydrogenated product of the copolymer block.
  • the methods a) to d) can be used alone or in combination.
  • the wiping direction was a direction in which the fiber was easily torn, the wiping load was 500 g, the stroke was 60 mm, the speed was 50 mm / sec, and the number of reciprocations was 20 reciprocations.
  • the L * value on the surface of the injection molded product was measured before and after the continuous friction work, and the amount of change was confirmed.
  • L * is a lightness index, which is L *, a *, and b * color system L * of CIE 1976, and was measured using S & M COLOR COMPUTER MODEL SM-5 manufactured by Suga Test Instruments Co., Ltd.
  • FT-IR Fourier transform infrared spectrophotometer
  • the sample adhering to the silicone stopper is dropped into the centrifuge tube using a small amount of acetone.
  • Two centrifuge tubes were set diagonally to the rotor of a Hitachi high-speed cooling centrifuge. The centrifuge was operated and centrifuged at 20000 rpm for 60 minutes. After completion of the centrifugation, the sedimentation tube was removed from the rotor, and the supernatant was decanted. About 20 ml of acetone was collected with a graduated cylinder, put into a centrifuge tube, sealed with a silicone stopper, and then shaken with a shaker for 1 hour. After repeating this operation once more, it was centrifuged at 20000 rpm for 50 minutes.
  • the sedimentation tube was removed from the rotor, and the supernatant was decanted. The same operation as the second decantation was performed once again. About 20 ml of methanol was collected with a graduated cylinder. Centrifuge for 30 minutes at 20000 rpm. After completion of the centrifugation, the sedimentation tube was removed from the rotor and the supernatant was decanted. After drying at 80 ° C. for 30 minutes, it was dried at 130 ° C. for 30 minutes. After drying, it was allowed to cool for 30 minutes or more in a desiccator. After sufficiently allowing to cool, it was precisely weighed to 0.1 mg with an electronic balance and calculated according to the following formula.
  • Acetone insoluble matter (mass%) [Acetone-insoluble content (g) / Sample collection amount (g)] ⁇ 100
  • Acetone insoluble content (mass%) [(acetone insoluble component including inorganic insoluble content (mass%) ⁇ inorganic insoluble content (mass%)) / (100% ⁇ inorganic insoluble content (mass%))] ⁇ 100
  • the inorganic insoluble here refers to, for example, titanium, glass fiber, talc, calcium carbonate, etc. used for the color pigment.
  • sliding agent used in the present Example is as follows.
  • ⁇ Sliding aid (C-1) Sanwa Kasei Kogyo Co., Ltd. sun wax E-250P (weight average molecular weight 1 million, acid value 20)
  • ⁇ Sliding aid (C-2) NUC3195 manufactured by Dow Chemical Japan Co., Ltd.
  • ⁇ Sliding aid (C-3) SAK-CS-PPT-1 manufactured by Shinagawa Chemical Co., Ltd.
  • the polymer (A-1) was 8.6% by mass of acrylonitrile, 57.1% by mass of butadiene, 34.3% by mass of styrene, The linear expansion coefficient was 16.0 ⁇ 10 ⁇ 5 / ° C., and the copolymer (B-1) was 20.1% by mass of acrylonitrile and 79.9% by mass of styrene, and (B-1) The reduced viscosity of was 0.33 dl / g.
  • FT-IR Fourier transform infrared spectrophotometer
  • the polymer (A-3) was found to be 21.9% by weight of acrylonitrile, 45.5% by weight of butadiene, 32.6% by weight of styrene, graft The ratio was 119.8%, the linear expansion coefficient was 13.9 ⁇ 10 ⁇ 5 / ° C., and the copolymer (B-3) was 39.8% by mass of acrylonitrile and 60.2% by mass of styrene, and (B-3) The reduced viscosity of was 0.33 dl / g.
  • FT-IR Fourier transform infrared spectrophotometer
  • the polymer (A-4) was 8.6% by mass of acrylonitrile, 68.1% by mass of butadiene, 23.3% by mass of styrene, graft The rate was 46.8%, the linear expansion coefficient was 17.9 ⁇ 10 ⁇ 5 / ° C., and the copolymer (B-4) was 27.1% by mass of acrylonitrile and 72.9% by mass of styrene, and (B-4) The reduced viscosity of was 0.38 dl / g.
  • FT-IR Fourier transform infrared spectrophotometer
  • the polymer (A-5) was 6.2% by mass of acrylonitrile, 77.1% by mass of butadiene, 16.7% by mass of styrene, The coefficient of expansion was 30.0%, the linear expansion coefficient was 19.4 ⁇ 10 ⁇ 5 / ° C., and the copolymer (B-5) was 27.0% by mass of acrylonitrile, 73.0% by mass of styrene, and (B-5) The reduced viscosity of was 0.36 dl / g.
  • FT-IR Fourier transform infrared spectrophotometer
  • the polymer (A-6) was 17.5% by mass of acrylonitrile, 35.0% by mass of butadiene, 47.5% by mass of styrene, and graft. The rate was 185.7%, the linear expansion coefficient was 12.2 ⁇ 10 ⁇ 5 / ° C., and the copolymer (B-6) was 27.1% by mass of acrylonitrile, 72.9% by mass of styrene, and (B-6) The reduced viscosity of was 0.33 dl / g.
  • FT-IR Fourier transform infrared spectrophotometer
  • the polymer (A-7) was 6.4% by mass of acrylonitrile, 68.3% by mass of butadiene, 25.3% by mass of styrene, 46.4% in rate, coefficient of linear expansion 12.9 ⁇ 10 ⁇ 5 / ° C.
  • copolymer (B-7) is 20.1% by mass of acrylonitrile, 79.9% by mass of styrene, and (B-7)
  • the reduced viscosity of was 0.34 dl / g.
  • the temperature was adjusted so that the solid content concentration at the tank outlet was 35%, and the phase conversion from liquid to solid was completed to form particles.
  • the number of stirrings in the first reaction tank was 90 revolutions / minute.
  • the solid content concentrations at the outlets of the second and third reaction tanks are 55 to 60% and 68 to 73%, respectively.
  • the temperature in the tank was adjusted and polymerization was continued.
  • the polymerization temperature was 130 ° C., and the same amount of the reaction solution as that of the supply solution was continuously withdrawn so that the filling rate of the reaction solution in the reaction vessel could be maintained at 70% by volume.
  • a jacket for temperature control was provided in a portion corresponding to the liquid phase portion of the reaction tank, and the jacket temperature was 128 ° C.
  • the power required for stirring was 4 kW / m, and the polymerization conversion rate was 39.8 wt% / hr.
  • the extracted reaction liquid was introduced into a volatile component removing apparatus maintained at 250 ° C. and a high vacuum of 10 mmHg, and the unreacted monomer and organic solvent were degassed and recovered, and the resulting copolymer (B-9) was recovered. Collected as pellets.
  • composition of (B-9) was 20.8% by mass of acrylonitrile and 79.2% by mass of styrene.
  • the reduced viscosity was 0.75 dl / g.
  • Rockwell hardness (M scale) of the copolymer (B-9) was measured and found to be 81.
  • the extracted reaction solution is introduced into a volatile component removing apparatus maintained at 250 ° C. and 10 mmHg in a high vacuum, and unreacted monomers and organic solvent are degassed and recovered, and the copolymer (B-10) is used as pellets. It was collected.
  • composition of (B-10) was 40.6% by mass of acrylonitrile and 59.4% by mass of styrene.
  • the reduced viscosity was 0.58 dl / g.
  • Rockwell hardness (M scale) of the copolymer (B-10) was measured and found to be 90.
  • the extracted reaction liquid is introduced into a volatile component removing apparatus maintained at 250 ° C. and a high vacuum of 10 mmHg, and unreacted monomers and organic solvent are degassed and recovered, and the copolymer (B-11) is formed into pellets. It was collected.
  • a Fourier transform infrared spectrophotometer FR-IR
  • the composition of (B-11) was 29.8% by mass of acrylonitrile and 70.2% by mass of styrene.
  • the reduced viscosity was 0.65 dl / g.
  • the Rockwell hardness (M scale) of the copolymer (B-11) was measured and found to be 83.
  • This solution was continuously supplied to a sealed pressure resistant reactor having an internal volume of 10 liters, and polymerized with stirring at an average temperature of 135 ° C. and an average residence time of 2 hours.
  • This polymerization solution is continuously sent to a storage tank connected to the reactor, the polymer is separated from the unreacted monomer and the solution, and the polymer is continuously extruded in a molten state by an extruder, and a copolymer ( A pellet of B-12) was obtained.
  • the extracted reaction solution is introduced into a volatile component removing apparatus maintained at 250 ° C. and 10 mmHg in a high vacuum, and unreacted monomers and organic solvent are degassed and recovered, and the copolymer (B-13) is formed into pellets. It was collected.
  • composition of (B-13) was 39.1% by mass of acrylonitrile, 51.1% by mass of styrene, 9.8% by mass of butyl acrylate. Met. The reduced viscosity was 0.42 dl / g. Further, the Rockwell hardness (M scale) of the copolymer (B-13) was measured and found to be 82.
  • the temperature is raised to 210 ° C.
  • the pressure is gradually reduced to 200 mmHg for 1 hour
  • the temperature is further raised to 240 ° C. for 20 minutes at 200 mmHg
  • the pressure is gradually reduced to 150 mmHg for 20 minutes, and further 100 mmHg.
  • the pressure was reduced to 20 mm and the reaction was reduced to 15 mmHg for 15 minutes
  • the temperature was raised to 280 ° C.
  • the pressure was finally reduced to 0.5 mmHg for 1.5 hours.
  • the intrinsic viscosity [IV] of the produced polycarbonate copolymer was measured in an methylene chloride (0.5 dl / g) at 20 ° C. using an Ubbelohde viscometer, it was 0.50 dl / g.
  • Nitrogen gas is blown into a 10 L jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank at a flow rate of 500 mL / min 1.099 g cupric chloride dihydrate, 4.705 g 35% hydrochloric acid, 41.971 g N, N, N ′, N′-tetramethylpropanediamine, 31.658 g di-n- Butylamine, 1264 g of n-butanol, 544 g of methanol, 3792 g of xylene, 136 g of 2,6-dimethylphenol, 24 g of 2,3,6-trimethylphenol were put into a homogeneous solution, and the internal temperature of the reactor was Stir until 40 ° C.
  • oxygen gas was introduced into the polymerization tank from the sparger at a rate of 1000 NmL / min into the vigorously stirred polymerization tank, and at the same time, 21.6 g of the mixed solution in the storage tank was used from the storage tank using a liquid feed pump. Sequentially added at a rate of / min. Aerated for 330 minutes, the internal temperature of the reactor was controlled to 40 ° C. In addition, 140 minutes after starting supply of oxygen gas, polyphenylene ether was precipitated to show a slurry form, and the addition of the mixed solution was completed before starting to show the slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization.
  • the internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum dried at 140 ° C. for 150 minutes to obtain polyphenylene ether.
  • 0.1 g of the obtained polyphenylene ether was dissolved in chloroform to prepare a solution having a concentration of 0.5 g / dl, and the reduced viscosity was measured and found to be 0.55 dl / g.
  • Rockwell hardness (M scale) of polyphenylene ether was measured, it was 80.
  • PCM- 30, L / D 28, manufactured by Ikekai Tekko Co., Ltd.
  • injection molding (EC100 manufactured by Toshiba Machine Co., Ltd.) was performed at a resin temperature of 250 ° C. and an injection speed of 20 mm / s to produce a flat plate of 10 cm ⁇ 10 cm ⁇ 3 mm.
  • the mold used was a 10000 count file polished until the surface had a Ra of 0.01 ⁇ m.
  • the mold temperature was 80 ° C.
  • Examples 2 to 13 Pellets and injection-molded products were obtained in the same manner as in Example 1 with the composition shown in Table 1.
  • Example 14 With the composition shown in Table 1, pellets and injection molded products were obtained in the same manner except that the injection speed of Example 1 was set to 5 mm / s. (Comparative Example 4) After obtaining pellets by the same method as in Example 1 with the composition shown in Table 1, injection molding was performed. The mold used was a file of 3500 count and polished until the surface became Ra 0.05 ⁇ m. The mold temperature was 80 ° C.
  • the injection-molded product of the present invention has no paint, high definition, and excellent effects of impact resistance and scratch resistance.
  • the injection-molded product of the present invention is high-definition and excellent in impact resistance, it can be used as a case for luxury home appliances, game machines, cameras, mobile phones and the like, decorative frames for televisions, and automobile interior members.
  • home appliances include televisions, telephones, printers, computers, vacuum cleaners, speakers, and the like.
  • automobile interior members include center clusters, switch boards, pillars, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne un objet moulé par injection, résistant aux chocs, très réfléchissant et dépourvu de revêtement qui comprend un ingrédient caoutchouc (A) et une résine thermoplastique (B), caractérisé en ce que (1) l'ingrédient caoutchouc (A) a été dispersé dans la résine thermoplastique (B), (2) l'ingrédient caoutchouc (A) a un coefficient d'expansion linéaire de 12,5×10-5 à 19×10-5 º/C, (3) la surface de l'objet moulé par injection a une clarté d'image réfléchie de 60 à 100 %, et (4) l'objet moulé par injection a une résistance au choc Charpy entaillé de 5 à 60 kJ/m2.
PCT/JP2011/072548 2010-10-01 2011-09-30 Objet moulé par injection, résistant aux chocs, très réfléchissant et dépourvu de revêtement et son processus de production WO2012043790A1 (fr)

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EP11829343.0A EP2623289A4 (fr) 2010-10-01 2011-09-30 Objet moulé par injection, résistant aux chocs, très réfléchissant et dépourvu de revêtement et son processus de production
CN201180047731.6A CN103153573B (zh) 2010-10-01 2011-09-30 未涂装的高鲜映性耐冲击注射成形品及其制造方法
US13/824,827 US9273204B2 (en) 2010-10-01 2011-09-30 Uncoated highly reflective impact-resistant injection-molded article and process for producing same
KR1020137006376A KR101466525B1 (ko) 2010-10-01 2011-09-30 무도장 고선영성 내충격 사출 성형품과 그 제조 방법
JP2012536578A JP5793501B2 (ja) 2010-10-01 2011-09-30 無塗装高鮮映耐衝撃射出成形品とその製造方法

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WO2013147143A1 (fr) * 2012-03-30 2013-10-03 旭化成ケミカルズ株式会社 Composition de résine et corps moulé à base de celle-ci
JP2013209513A (ja) * 2012-03-30 2013-10-10 Asahi Kasei Chemicals Corp 無塗装高鮮映難燃耐衝撃射出成形品とその製造方法
WO2014189121A1 (fr) 2013-05-23 2014-11-27 旭化成ケミカルズ株式会社 Composition de résine thermoplastique et article moulé en celle-ci

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KR101811551B1 (ko) * 2013-11-11 2017-12-21 아사히 가세이 가부시키가이샤 자동차 내장 부품
US10619432B2 (en) 2017-05-17 2020-04-14 Saudi Arabian Oil Company Oil-swellable, surface-treated elastomeric polymer and methods of using the same for controlling losses of non-aqueous wellbore treatment fluids to the subterranean formation
US10081756B1 (en) 2017-05-17 2018-09-25 Saudi Arabian Oil Company Loss circulation material composition comprising oil-swellable and desolvated polymer gels
JP6938753B1 (ja) * 2020-12-23 2021-09-22 テクノＵｍｇ株式会社 めっき用樹脂組成物

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Publication number Priority date Publication date Assignee Title
WO2013022084A1 (fr) * 2011-08-11 2013-02-14 旭化成ケミカルズ株式会社 Boîtier non revêtu et son procédé de fabrication
US9187626B2 (en) 2011-08-11 2015-11-17 Asahi Kasei Chemicals Corporation Uncoated housing and method for manufacturing same
WO2013147143A1 (fr) * 2012-03-30 2013-10-03 旭化成ケミカルズ株式会社 Composition de résine et corps moulé à base de celle-ci
JP2013209513A (ja) * 2012-03-30 2013-10-10 Asahi Kasei Chemicals Corp 無塗装高鮮映難燃耐衝撃射出成形品とその製造方法
WO2014189121A1 (fr) 2013-05-23 2014-11-27 旭化成ケミカルズ株式会社 Composition de résine thermoplastique et article moulé en celle-ci

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US9273204B2 (en) 2016-03-01
KR20130041331A (ko) 2013-04-24
US20130184409A1 (en) 2013-07-18
KR101466525B1 (ko) 2014-11-27
EP2623289A4 (fr) 2016-08-24
CN103153573B (zh) 2016-06-15

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